Hydrogen tank system based on high-surface materials used for intermediate storage of excess hydrogen gas in stationary applications

ABSTRACT

A hydrogen tank system for collectably storing of excess hydrogen. The hydrogen tank system consists of a primary tank apparatus and a cryoadsorption hydrogen storage apparatus, as well as tubing, detectors, valves, and regulators required to manage the collection and storage of excess hydrogen gas generated during operation, as well as to manage distribution of hydrogen gas to one or more functional modules, such as a stationary fuel cell.

TECHNICAL FIELD

The present invention relates to the storage and manipulation of gases, and more particularly to the storage and control of excess hydrogen gas produced by boil-off and mass transfer losses from stationary storage and filling systems.

BACKGROUND OF THE INVENTION

Hydrogen storage technology is a necessary prerequisite for the development of many advances in the area of alternative fuel sources. Hydrogen is the cleanest and most abundant of these energy sources. In particular, mobile applications, such as hydrogen-propelled vehicles, place a demand on the infrastructure to provide safe, efficient, and inexpensive delivery of hydrogen to the end user.

A number of current storage technologies are available. Compressed gaseous hydrogen (CGH₂) involves storage of hydrogen gas under high pressures of for example between 35 and 70 MPa. Liquid hydrogen (LH₂) involves storage of liquefied hydrogen gas. These technologies involve several technical challenges, notably low storage densities, in the case of both methods, and hydrogen boil-off in the case of LH₂.

An alternative storage mechanism is provided by the physisorption of hydrogen molecules on high-surface materials like activated carbons, zeoliths, metal-organic frameworks (MOFs) or polymers of intrinsic microporosity (PIMs). Since the interaction of the hydrogen and the substrate material is quite weak, it is necessary to apply operating pressures from 10 to 50 bar and operating temperatures of about 25K to 150K.

During the operation of the filling facility, particularly the refilling of LH₂ into a primary tank apparatus, some hydrogen can be lost to the environment. This occurs primarily because the associated pipes and machinery have to be cooled down toward 20K, but also for fundamental thermodynamic reasons. The losses from boil-off, tanking, and other mass transfer activities have to be minimized for commercial, safety, and environmental reasons.

A customer might be required to pay for the lost hydrogen during re-filling. Alternatively, the operator of the station may be required to absorb these losses. Therefore, it is very attractive from a commercial standpoint to minimize these losses as much as possible.

For safety reasons, hydrogen should not be released into the environment of a pump. Under certain conditions, this can create a fire or an explosive hazard. Hydrogen could react exothermically with oxygen to form water and to release large amounts of energy, as for example in a fire or in an explosion. From a safety standpoint limiting the amounts of hydrogen gas released will drastically reduce the oxygen reaction hazards.

Hydrogen release may also have environmental effects. Hydrogen gas that is lost during refilling or as boil-off could reach the upper atmosphere. Here it could react via a complex chemical reaction with ozone to form water, thereby decomposing critical atmospheric ozone. This consequence would also be limited by preventing release of hydrogen.

Another consideration in the construction of a stationary fueling application is the stability of the flow rate. Some of the stationary applications, such as a stationary internal combustion engine (ICE) or a stationary fuel cell, require a stable flow of hydrogen gas to operate effectively. Excess hydrogen gas generated through mass transfer and spot heating could disrupt the orderly flow of hydrogen gas to these applications.

Some attempts have been made to remedy these effects. Re-liquefaction would help mitigate some of these factors but would be very expensive and require additional equipment. Compression would also be expensive and require additional equipment. Catalytic burning of the lost hydrogen has also been proposed, but this is wasteful since the resulting water cannot, itself, be used for energy generation.

Therefore, what remains needed in the art is a means of controlling the excess hydrogen gas produced through its use as a fuel in stationary applications.

SUMMARY OF THE INVENTION

The present invention is a hydrogen tank system designed to collect, store and transfer excess hydrogen gas that has been generated in the normal course of the operation of a hydrogen fueled stationary application. Within the framework of this invention, a cryoadsorption hydrogen storage apparatus is added to the conventional setup of a stationary hydrogen fueled application, such as a hydrogen filling station. The hydrogen tank system would serve as a hydrogen collection system, an intermediate hydrogen storage system, and a hydrogen transfer system to cope with the amount of excess hydrogen gas generated during the normal activities of hydrogen delivery, such as a hydrogen filling station for filling of LH₂ vehicles, during boil-off mode of the main LH₂ storage tank, etc. Further, the cryoadsorption hydrogen storage apparatus may serve as a reserve tank, which may be utilized in mobile as well as stationary applications.

Other stationary applications of hydrogen fueling impose more stringent requirements in the management of excess released hydrogen gas. More involved stationary applications, such as those that include stationary internal combustion engines or stationary fuel cells, require a relatively stable flow of hydrogen gas. The intermediate storage system according to the present invention will smooth the flow rate of outgoing hydrogen and therefore will address this problem.

The hydrogen tank system according to the present invention is designed in such a way as to minimize mass transfer losses of hydrogen from the system into the environment and to minimize heat transfer from the environment into the system.

The hydrogen tank system consists of a primary tank apparatus and the above referenced cryoadsorption hydrogen storage apparatus, as well as tubing, detectors, valves, and regulators required to manage the collection, storage and transfer of the excess hydrogen gas.

The primary tank apparatus consists of at least one liquid hydrogen (LH₂) storage tank, conventional in the art, as well as the required tubes, hoses, valves and regulators necessary to connect the primary tank apparatus to the cryoadsorption hydrogen storage apparatus. The LH₂ can be dispensed directly from the primary tank apparatus to an external tank, such as for example the fuel tank of a mobile hydrogen fueled device. In the operation of the hydrogen tank system, excess hydrogen gas will inevitably be produced; however, this excess hydrogen gas is collected by the cryoadsorption hydrogen storage apparatus.

The cryoadsorption hydrogen storage apparatus can consist of a single cryoadsorption unit, or a group thereof configured in series, in parallel, or in a more general topological structure. The cryoadsorption units are connected by means of pipes or tubes and controlled via valves. Particular elements of the piping aid in the modulation of temperature in the cryoadsorption units.

The hydrogen tank system additionally provides means to transfer hydrogen gas from the cryoadsorption hydrogen storage apparatus to external functional modules. These functional modules can be stationary hydrogen-fueled applications, such as for example stationary internal combustion engines, stationary fuel cells, other devices, such as re-liquifiers, compressors or other cryoadsorption units, or even mobile fuel tanks. Each of these functional modules is connected by means of pipes and tubes to the primary storage tank, the cryoadsorption hydrogen storage apparatus, or both.

Accordingly, it is an object of the present invention to provide a means to collect, store and transfer excess hydrogen gas which evolves in the normal operation of stationary devices fueled by a hydrogen tank system.

This and additional objects, features and advantages of the present invention will become clearer from the following specification of a preferred embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram of a hydrogen tank system consisting of a primary tank apparatus and a cryoadsorption hydrogen storage apparatus, configured to supply hydrogen gas to functional modules.

FIG. 2A is a schematic representation of a configuration of valves and pipes for a single cryoadsorption unit to process excess hydrogen gas produced in normal boil-off and during fueling operations.

FIG. 2B is a schematic representation of the same system as seen in FIG. 2A, wherein now the valves are set for de-fueling the cryoadsorption unit.

FIGS. 3A and 3B are topological diagrams showing two different topologies of a cryoadsorption hydrogen storage apparatus according to the present invention.

FIG. 4 is a diagram showing an example of regulation of hydrogen gas flow from a cryoadsorption hydrogen storage apparatus to functional modules which require stable flow of hydrogen gas, according to the present invention.

FIG. 5 is a block diagram showing a family of functional modules associated with a cryoadsorption hydrogen storage apparatus according to the present invention.

FIGS. 5A and 5B are schematic representations showing further detail of certain of the functional modules of FIG. 5.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Referring now to the Drawing, FIGS. 1 through 5B depict aspects of a hydrogen tank system 100 according to the present invention, which is configured to collect, store and transfer excess hydrogen gas that has been generated in the normal course of operation. The following description of the preferred embodiment is merely exemplary in nature and is not intended to limit the invention, its applications, or its uses.

With reference to FIG. 1, the hydrogen tank system 100 consists of a primary tank apparatus 102 and a cryoadsorption hydrogen storage apparatus 104, either of which being connectable to various functional modules 106.

With reference to FIG. 2A, a hydrogen tank system 100′ is shown which is configured for managing boil-off or tanking (filling) hydrogen losses, and has a cryoadsorption hydrogen storage apparatus 104 in the form of a single cryoadsorption unit 112 cooled to approximately 20K by hydrogen gas from the primary tank apparatus 102. An inlet pipe 114 runs selectively between the primary tank apparatus 102 and the cryoadsorption unit 112, a cooling jacket 118 of the the cryoadsorption unit, and the functional modules 106. In this regard, the inlet pipe 114 branches into three parts, a first supply pipe 114 a for the cooling jacket 118 of the cryoadsorption unit 112, a second supply pipe 114 b for the cryoadsorption unit 112, and a third supply pipe 114 c that runs directly to the functional modules 106. Each of these supply pipes is regulated individually by means of supply valves, namely a first supply valve 126 a for the cooling jacket 118, a second supply valve 126 b for the cryoadsorption unit 112, and a third supply valve 126 c for the functional modules 106.

The first supply valve 126 a to the cooling jacket 118 and the second supply valve 126 b to the cryoadsorption unit 112 are both open and the third supply valve 126 c to the functional modules 106 is closed. The cooling jacket 118 is vented by means of an outlet pipe 128 connected to the functional modules 106. The cryoadsorption unit 112 is connected to the functional modules 106 by means of a outlet pipe 130 regulated by a functional module control valve 132, which is closed. Further in this configuration of the hydrogen tank system 100′, hydrogen gas released from the storage tank apparatus 102 is routed to the cryoadsorption unit 112 and to the cooling jacket 118. Direct flow to the functional modules 106 is prevented.

With reference to FIG. 2B, the hydrogen tank apparatus 100′ is now configured to de-fuel the cryoadsorption unit 112. The only difference between this and the cryoadsorption hydrogen storage apparatus 104 of FIG. 2A which is configured to manage boil-off and other excess hydrogen gas generation, is the settings of the valves. In this case, the first and second supply valves 126 a, 126 b for the cooling jacket 118 and the cryoadsorption unit 112, respectively, are now both closed, while the third supply valve 126 c (between the inlet pipe 114 and the functional modules 106) and the functional module control valve 132 are now both open. In this configuration of the hydrogen tank apparatus 100′, hydrogen gas released from the primary tank apparatus 102 and the cryoadsorption unit 112 is released to the functional modules 106. Flow of hydrogen gas from the primary tank apparatus 102 to the cooling jacket 118 or the cryoadsorption unit 112 is prevented.

Hydrogen gas is released from the cryoadsorption units by applying heat via, for example, an electrical heater of a heat exchanger with the external environment, by reducing the operating pressure, or a combination of both. The materials used, the structural design, and techniques of operation of the cryoadsorption units of the cryoadsorption hydrogen storage apparatus are exemplified in U.S. patent application Ser. No. 11/348,107, filed on Feb. 6, 2006, which disclosure is hereby herein incorporated by reference.

In order to increase the hydrogen collection capacity of the hydrogen tank system according to the present invention, additional cryoadsorption units may be added. With reference to FIG. 3A, a plurality of cryoadsorption units (CAU) 112 a, 112 b, 112 c are configured in series by means of tubing or pipe to each other singly in the direction of the flow of the hydrogen gas. In FIG. 3B, a group of cryoadsorption units (CAU) 112 a′ and 112 e′ are connected in series with a parallel arrangement of cryoadsorption units 112 b′, 112 c and 112 d′ by means of pipes or tubes. More complicated topologies for arranging the cryoadsorption units may be used according to the present invention. The cryoadsorption units may be insulated individually, as a group, or share insulation with the primary tank apparatus 102. The insulation may be multi-layer super insulation, powder vacuum insulation and have a liquid nitrogen active cooling shield.

Certain types of the functional modules 106 require a carefully regulated flow of hydrogen gas. With reference to FIG. 4, a cryoadsorption unit 112 is connected by means of an outlet tube 130 to a functional module 106. The flow of hydrogen is controlled by a feedback system 134 conventional in the art. The feedback system 134 regulates the flow of hydrogen gas by adjustments to the functional module control valve 132, to compensate for deviations from the target flow rate as detected by a hydrogen gas flow sensor 136.

With reference to FIG. 5, a family of functional modules 106 shows a range of device types that may be included in the present invention. This may include hydrogen fueled stationary applications, such as stationary internal combustion engines 106 d and stationary fuel cells 106 c. This may further include a functional module 106 b which recycles hydrogen gas to the primary tank apparatus 102 including a re-liquefier 138, as shown at FIG. 5A. This may also include an alternate means of hydrogen dispensing 106 a including compressor 140 tied to a compressed hydrogen gas (CGH₂) dispenser 142, as shown at FIG. 5B.

To those skilled in the art to which this invention appertains, the above described preferred embodiment may be subject to change or modification. Such change or modification can be carried out without departing from the scope of the invention, which is intended to be limited only by the scope of the appended claims. 

1. A hydrogen tank system comprising: a primary tank apparatus including at least one tank for holding liquid hydrogen, wherein an excess hydrogen gas is derived from a portion of the liquid hydrogen; and a cryoadsorption hydrogen storage apparatus comprising at least one cryoadsorption unit, said cryoadsorption hydrogen storage apparatus being connected to said primary tank apparatus; wherein the excess hydrogen gas is storably absorbed by said cryoadsorption hydrogen storage apparatus.
 2. The system of claim 1, wherein said at least one cryoadsorption unit comprises a plurality of cryoadsorption units mutually arranged in a predetermined mutually interconnected configuration.
 3. A hydrogen tank system comprising: a primary tank apparatus including at least one tank for holding liquid hydrogen, wherein an excess hydrogen gas is derived from a portion of the liquid hydrogen; a cryoadsorption hydrogen storage apparatus comprising at least one cryoadsorption unit, said cryoadsorption hydrogen storage apparatus being connected to said primary tank apparatus; and means for selectively connecting at least one functional module to said primary tank apparatus and said cryoadsorption storage apparatus; wherein the excess hydrogen gas is storably absorbed by said cryoadsorption hydrogen storage apparatus.
 4. The system of claim 3, wherein said means connects said primary tank apparatus to said at least one functional module.
 5. The system of claim 3, wherein said means connects said at least one cryoadsorption unit to said at least one functional module.
 6. The system of claim 3, wherein said means connects said at least one cryoadsorption unit and said primary tank apparatus to said at least one functional module.
 7. The system of claim 3, wherein said at least one cryoadsorption unit comprises a plurality of cryoadsorption units mutually arranged in a predetermined mutually interconnected configuration.
 8. The system of claim 7, wherein said means connects said primary tank apparatus to said at least one functional module.
 9. The system of claim 7, wherein said means connects said at least one cryoadsorption unit to said at least one functional module.
 10. The system of claim 7, wherein said means connects said at least one cryoadsorption unit and said primary tank apparatus to said at least one functional module.
 11. A method for controlling hydrogen gas exiting a primary tank apparatus for holding liquid hydrogen, comprising the steps of: connecting at least one cryoadsorption unit to the primary tank apparatus; and collecting boil-off hydrogen gas exiting the primary tank apparatus storably in the at least one cryoadsorption unit.
 12. The method of claim 11, further comprising: sending hydrogen gas exiting the primary tank apparatus to at least one functional module.
 13. The method of claim 12, further comprising: sending the collected boil-off hydrogen gas stored in the at least one cryoadsorption unit to the at least one functional module.
 14. The method of claim 11, further comprising: collecting hydrogen gas other than the boil-off hydrogen gas in the at least one cryoadsorption unit.
 15. The method of claim 14, further comprising: sending hydrogen gas from the primary tank apparatus to at least one functional module.
 16. The method of claim 15, further comprising: sending the collected hydrogen gas stored in the at least one cryoadsorption unit to the at least one functional module.
 17. The method of claim 16, wherein said steps of sending hydrogen gas from the primary tank apparatus and sending the collected hydrogen gas stored in the at least one cryoadsorption unit further comprise: sending hydrogen gas to the at least one functional module at a predetermined rate, wherein hydrogen gas is selectively collected and selectively stored in the at least one cryoadsorption unit so as to provide said predetermined rate.
 18. The method of claim 14, further comprising: sending the collected hydrogen gas stored in the at least one cryoadsorption unit to the at least one functional module. 